Allylated di or polycyclopentadiene diphenols and thermosettable compositions containing same

ABSTRACT

New compositions of matter are disclosed which are allylated di and polycyclopentadiene diphenols. These new compositions are useful in thermoset resin compositions comprising styrene, a dicyclopentadiene-modified unsaturated polyesteramide and said allylated di and polycyclopentadiene diphenol(s).

CROSS REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part of copending application Ser.No. 446,090 filed Dec. 2, 1982, now abandoned.

BACKGROUND OF THE INVENTION

The present invention pertains to new compositions of matter and tonovel thermosettable compositions containing them.

Thermosettable compositions such as unsaturated polyester resins,dicyclopentadiene modified unsaturated polyester resins, unsaturatedpolyesteramide resins, dicyclopentadiene modified unsaturatedpolyesteramide resins, vinyl ester resins and the like are well known.Such resins can be employed as is, but are usually diluted with apolymerizable unsaturated monomer such as styrene. These resins areuseful in the preparation of castings, laminates, coatings, and thelike. However, such resins create relatively large exotherms uponcuring, usually with peroxide curing agents, which can induce crackingor fracturing of the cured part, as well as excessive volatile monomerloss.

The present invention provides a thermosettable resin composition whichhas reduced exotherm temperatures without an unacceptable low reactivityrate and in many instances, the cured resin has an improvement in one ormore properties such as heat distortion temperature, hardness, tensilestrength, elongation, resistance to thermal aging and the like.

SUMMARY OF THE INVENTION

The present invention is directed to new compositions of matterrepresented by the formulas ##STR1## wherein each A is independently agroup represented by the formulas --CH₂ --CH═CH₂ or ##STR2## each X is ahalogen, preferably chlorine or bromine and each n independently has anaverage value from zero to about 20, preferably from zero to about 8.

All of the compositions represented by Formulas I, II, III, IV, V, VI,VII, and VIII are isomeric mixtures wherein the substitution of thephenolic groups by dicyclopentadiene is in the ortho and para positions.In compositions represented by Formulas II, III, IV, V, VI, VII, andVIII thermally induced Claisen rearrangement has occurred and the allylgroup(s) on the aromatic ring are thus ortho or para to the ether-linkedallyl group(s) and/or the free phenolic hydroxyl group(s).

Minor amounts (5 to 6%) of allylated monophenols, isomeric triphenols,and bis(dicyclopentadienyl)diphenols are also present in thesecompositions and are represented by Formulas IX, X, and XI. It is to beunderstood that under conditions of thermally induced Claisenrearrangement, the allyl ether group(s) in Formulas IX, X and XI migrateto provide allyl group(s) on the aromatic ring which are ortho or parato the free phenolic hydroxyl group(s) (or ether-linked allyl group(s)if additional allylation reaction is performed). These are present indirect proportion to the amount of each respective non-allylatedphenolic that was present as a part of the original dicyclopentadienediphenol reactant.

The present invention also concerns a composition which isthermosettable upon curing with a curing quantity of a suitable curingagent, which thermosettable composition comprises,

(1) from 5 to about 95, preferably from about 20 to about 80, mostpreferably from about 45 to about 70, percent by weight (pbw) of atleast one resin composition selected from the group consisting of

(a) unsaturated polyester resins,

(b) unsaturated polyesteramide resins,

(c) dicyclopentadiene modified unsaturated polyester resins,

(d) dicyclopentadiene modified unsaturated polyesteramide resins, and

(e) vinyl ester resins,

(2) from zero to about 95, preferably from about 70 to about 20, mostpreferably from about 30 to about 55, pbw of at least one polymerizableethylenically unsaturated monomer; and

(3) from about 1 to about 50, preferably from about 1 to about 30, mostpreferably from about 3 to about 15 pbw of a composition represented bythe aforementioned formulas I through XI.

DETAILED DESCRIPTION OF THE INVENTION

The allylated dicyclopentadiene or polycyclopentadiene diphenols can beprepared by the transcarbonation process wherein allylmethyl carbonateor a crude mixture containing allylmethyl carbonate is reacted with thedicyclopentadiene diphenol(s) in the presence of a catalytic amount ofpalladium on carbon and triphenylphosphine. Although less preferred, theallylated dicyclopentadiene diphenols can be prepared by the directallylation of the dicyclopentadiene diphenol(s) with an allyl halidesuch as allyl chloride in the presence of an alkaline agent such as anaqueous solution of alkali metal hydroxide. Preferred alkali metalhydroxides include sodium hydroxide and potassium hydroxide. Reactiontemperatures of from about 25° to about 150° C. are operable withtemperatures of 50° to 100° C. being preferred. If desired, inertsolvents such as 1,4-dioxane and phase transfer catalysts such asbenzyltrialkylammonium halides or tetraalkylammonium halides can beemployed.

The compositions wherein A is ##STR3## can be prepared by halogenationof the compositions wherein A is an allyl group. The halogenation iscarried out in a solvent suitable for the allylated dicyclopentadiene orpolycyclopentadiene diphenol. One useful solvent is methylene chloride.The solution is maintained at minus 20° C. to 50° C. and preferablyminus 10° to 25° C. The solution is sparged with nitrogen, the halogen,preferably bromine, is added dropwise with stirring while maintainingreaction temperature. Less than stoichiometric amounts of halogen can beused to control the amount of halogen as well as the amount of unreactedallyl groups in the product. It is frequently desireable to maintain thereaction mixture for a period of at least about one-half hour afterhalogen addition is complete. It may be of advantage to add an oxiranecompound, such as an epoxide or polyepoxide, as a hydrohalide scavengerto aid in stabilization of the product. Removal of the solvent, forexample, using distillation under reduced pressure, provides the finalproduct.

Useful products are prepared wherein all or a part of the allyl groupsare halogenated. Said products are useful as reactive additives for fireretardant polymers. If all of the allyl groups are completelyhalogenated, these halogenated products become useful as a non-reactive(no polymerizable allyl groups) additive for fire retardant polymers.

Polycyclopentadiene can be prepared by heating cyclopentadiene attemperatures above 100° C. as disclosed by Kirk-Othmer, ENCYCLOPEDIA OFCHEMICAL TECHNOLOGY, Third Edition, Vol. 7, pp. 417-419 (1979), which isincorporated herein by reference.

The dicyclopentadiene or polycyclopentadiene diphenol starting materialswhich are allylated to prepare the compositions of the present inventioncan be prepared by methods taught in U.S. Pat. No. 3,419,624 which isincorporated herein by reference. In a more preferred preparation,phenol is added to a reactor and maintained at 45° C. with stirringunder a nitrogen atmosphere. An acidic catalyst, such as Filtrol 1 (anacidified clay manufactured by Filtrol Corporation) is added to thereactor. Dicyclopentadiene (DCPD) is added over a 2.5 to 3.0 hour (9000to 10,800 s) period so that the reaction temperature reaches 80° C. bythe end of the DCPD addition. A molar ratio of phenol to DCPD of about10 to 1 is preferred while a molar ratio of 20 to 1 is most preferred.The reaction temperature is increased to 150° C. until completion of thereaction, typically about 3.0 hours (10,800 s). The progress of thereaction can be monitored by flame ionization gas chromatography. Thereactor is cooled to 60° C. and the catalyst is removed by filtration.The filtrate is vacuum distilled reaching a maximum pot temperature of240° C. at 20 to 0.5 mm Hg. This removes excess phenol and anydicyclopentadienyl monophenols. The dicyclopentadiene diphenol isremoved in 80% yield as a transparent yellow to orange-colored solid.This product contains about 5% higher molecular weight components asdetermined by gel permeation chromatography. By way of contrast,dicyclopentadiene diphenol prepared using the teachings of U.S. Pat. No.3,419,624 (i.e., using an acid ion exchange resin catalyst) is of a darkcolor with cloudiness and contains over 10% higher molecular weightcomponents. Polydicyclopentadiene diphenol is obtained by substitutingpolydicyclopentadiene for dicyclopentadiene in this preparation.

The norbornyl (dicyclopentadiene) modified unsaturated polyesteramidesused herein can be prepared by the methods described herein and they arefurther described in patent application Ser. No. 333,221, filed Dec. 21,1981.

The norbornyl modified unsaturated polyesters used herein can beprepared by the methods described in U.S. Pat. Nos. 4,189,548 or4,167,542 and 4,148,765.

The unsaturated polyester resins suitable for use herein are well knownand are described in Kirk-Othmer Encyclopedia of Chemical Technology,3rd edition, pp. 575-594 which is incorporated herein by reference.

The unsaturated polyesteramide resins suitable for use herein areprepared by substitution of a portion of the polyol used in theunsaturated polyester resin preparation with a suitable polyamine ormixture of polyamines.

The polyols used in either unsaturated polyesters or unsaturatedpolyesteramides are from the class of those having the formula:HO--R--OH where R is a divalent organic radical selected from the groupconsisting of alkylene, ether-linked alkylene, ether-linked arylene,cycloalkylene, polycycloalkylene, bis(alkyl)cycloalkylene,bis(alkyl)polycycloalkylene, and arylene. Mixtures of two or more ofsuch polyols can also be used.

The polyamines used to make unsaturated polyesteramides are from theclass of those having the formula: ##STR4## wherein R₁ and R₂ areindependently selected from the group consisting of hydrogen, aliphatic,cycloaliphatic and aromatic radicals, or R₁ and R₂ taken together withthe remainder of the molecule form an aliphatic ring; and R₃ is adivalent organic radical selected from the group consisting of alkylene,ether-linked alkylene, ether-linked arylene, alkylene amino-linkedalkylene, alkylene amino-linked cycloalkylene, cycloalkylene,polycycloalkylene, arylene, alkylarylene, bis(alkyl)cycloalkylene andbis(alkyl)polycycloalkylene. Mixtures of two or more of such polyaminescan also be used.

Typical diamines that are useful are ethylene diamine, propylenediamine, hexane-1,6-diamine, piperazine,4,4'-methylenebis(cyclohexylamine), 2,2'-bis(4-aminocyclohexyl)propane,4,4'-diaminodiphenyl ether, bis(aminomethyl)norbornane, toluene diamine,bis(aminomethyl)dicyclopentadiene and homopiperazine. Typical polyaminesare aminoethylpiperazine and diethylenetriamine.

Representative of the useful diols are: ethylene glycol, propyleneglycol, diethylene glycol, dipropylene glycol, dicyclopentadienedimethanol, bis(hydroxymethyl)norbornane, methyl cyclohexanedimethanol,bis(hydroxypropyl)bisphenol A and other hydroxyalkylated bisphenols.Typical polyols are pentaerythritol and glycerine propoxylates.

The α,β-unsaturated polycarboxylic acid is preferably maleic acid,fumaric acid, the anhydride of maleic acid or mixtures of thesecompounds. Such acids are readily available, have good reactivity withthe diol and/or the diamine, and result in products of good properties.Other less preferred unsaturated polycarboxylic acids include itaconicacid, citraconic acid, and the like.

Part of the α,β-unsaturated polycarboxylic acid may be replaced with asaturated or aromatic polycarboxylic acid to vary the crosslinkingpotential and physical properties of the unsaturated polyester orpolyesteramide. Such acids include the aliphatic acids such as adipicacid and the aromatic acids such as isophthalic acid. Replacement ofpart of the α,β-unsaturated acid with such acids is commonplace in thepolyester art. Suitable selection of the acid and the amount necessaryto achieve a desired purpose will be known to the skilled worker and canbe optimized with simple preliminary experiments.

The total amount of acid varies as a function of the total polyol ormixture of polyol and polyamine and, optionally, norbornyl ingredientsused.

The terminal group used to modify the unsaturated polyester orpolyesteramide is a norbornyl radical. Dicyclopentadiene (DCPD) ordicyclopentadiene concentrates are most preferred norbornyl functionalmaterials to be employed in terminating one or both ends of the chain.Polycyclopentadiene (i.e., DCPD oligomers) or dicyclopentadienemonoalcohol are also preferred species.

DCPD is sold commercially as a product of about 97 or greater percentpurity. It is also sold as a C₁₀ hydrocarbon concentrate prepared bydimerizing a crude C₅ stream from the cracking of hydrocarbons as taughtin U.S. Pat. No. 3,557,239.

Examples of some of the dimers which have been identified in theseconcentrates are the Diels-Alder adducts of two moles of isoprene(isoprene dimers), the adduct of cyclopentadiene and isoprene, theadduct of cyclopentadiene and piperylene and the like.

Either the dicyclopentadiene concentrate or the relatively pure DCPD maybe employed in preparing the modified polyesters or polyesteramides.

The modified unsaturated polyesters or polyesteramides can be preparedby a variety of techniques. In a preferred method, moltenα,β-unsaturated carboxylic anhydride is partially hydrolyzed with lessthan the stoichiometric equivalent of water and reacted with thenorbornyl derivative to form esters of that derivative and containingunesterified acid and anhydride. This reaction may conveniently beperformed in stages whereby a reactant is added stepwise to controlreaction exotherms. The product mixture is then reacted with the polyoland polyamine or the polyol alone to result in the desired modifiedunsaturated polyester or polyesteramide.

In a typical procedure, molten maleic anhydride and a fraction of thestoichiometric equivalent of water is maintained at an elevatedtemperature of from about 60° to 130° C. The initial fractionalequivalent of dicyclopentadiene (DCPD) is then added and allowed toreact. A second fractional equivalent of water and of DCPD is added andallowed to react. Additional fractional equivalents of DCPD are addedand each allowed to react before addition of the next increment untilthe desired amount of DCPD has been added. The number of fractionalequivalents can be increased and the size of each fractional equivalentcorrespondingly decreased to any desired number of fractionalequivalents, including continuous addition. The relative size of thefractional equivalents can vary.

The amount of maleic (or other) anhydride employed in this firstesterification step may be equal to the equivalent of DCPD in whichevent the product is essentially all ester. Alternatively, the amount ofanhydride may be the equivalent needed to make the ester plus thatexcess that is to be used in the subsequent esterification oresteramidation step.

To the mixture of esterified DCPD and acid and/or anhydride is added thepolyol and polyamine or the polyol alone. After addition of the polyoland polyamine or the polyol alone is complete, the reaction can bedriven to maximum yield by maintaining or increasing the temperatureuntil the desired acid number has been reached. Typically, acid numbersof 15 to 35 are preferred, with acid numbers of 15 to 25 being mostpreferred; although acid numbers that are higher or lower may betolerated, and, in some instances, may be desired.

In an equally preferred method, molten α,β-unsaturated carboxylicanhydride is essentially totally hydrolyzed with a stoichiometric orgreater equivalent of water and reacted with the norbornyl derivative toform esters of that derivative and containing unesterified acid. Thisreaction may conveniently be performed in stages whereby a reactant isadded stepwise, controlling reaction exotherms. The product mixture isthen reacted with the polyol and polyamine or the polyol alone to resultin the desired modified unsaturated polyester or polyesteramide.

In a typical procedure, molten maleic anhydride and the stoichiometricor greater equivalent of water are maintained at an elevated temperaturefrom about 50° to 150° C. The temperature is allowed to stabilize atabout 120° to 125° C. and the initial fractional equivalent of DCPD isthen added and allowed to react. A second fractional equivalent of DCPDis added and allowed to react. Additional fractional equivalents of DCPDare added and each allowed to react before addition of the nextincrement until the desired amount of DCPD has been added.

The amount of maleic (or other) anhydride employed in this firstesterification step may be equal to the equivalent of DCPD in whichevent the product is essentially all ester. Alternatively, the amount ofanhydride may be the equivalent needed to make the ester plus thatexcess that is to be used in the subsequent esterification oresteramidation step.

The polyol and polyamine or the polyol alone are added to the mixture ofesterified DCPD and acid as previously described.

Many other alternate methods will be recognized by the skilled worker.For example, molten maleic anhydride may be added to a mixture of DCPDand water in a reactor. The polyol and polyamine or the polyol alone areadded to the mixture of esterified DCPD and acid and/or anhydride asbefore. Finally, although less preferred, DCPD, maleic anhydride, waterand the polyol and polyamine or polyol alone may be simultaneouslyreacted.

The vinyl ester resins (VER) useful herein are a well known class ofresins made from unsaturated carboxylic acids and polyepoxides. Vinylester resins are the reaction product of about equivalent amounts of amonounsaturated monocarboxylic acid and a polyepoxide. One class of VERis described in U.S. Pat. No. 3,367,992 where dicarboxylic acid halfesters of hydroxyalkyl acrylates or methacrylates are reacted withpolyepoxide resins. Bowen in U.S. Pat. Nos. 3,066,122 and 3,179,623describes the preparation of VER from monocarboxylic acids such asacrylic and methacrylic acid. Bowen also describes alternate methods ofpreparation wherein a glycidyl methacrylate or acrylate is reacted withthe sodium salt of a dihydric phenol such as bisphenol A. VER based onepoxy novolac resins are described in U.S. Pat. No. 3,301,743 to Fekete,et al. Fekete, et al describe VER where the molecular weight of thepolyepoxide is increased by reacting a dicarboxylic acid with thepolyepoxide resin as well as acrylic acid, etc. in U.S. Pat. No.3,256,226. Other difunctional compounds containing a group which isreactive with an epoxide group, such as an amine, mercaptan, and thelike, may be utilized in place of the dicarboxylic acid. All of theabove-described resins, which contain the characteristic linkage##STR5## and terminal polymerizable vinylidene groups are classified asVER and are incorporated by reference.

Briefly, any of the known polyepoxides may be employed in thepreparation of the vinyl ester resins. Useful polyepoxides are glycidylpolyethers of both polyhydric alcohols and polyhydric phenols, such asthe diglycidyl ether of bisphenol A, epoxy novolacs, epoxidized fattyacids or drying oil acids, epoxidized diolefins, epoxidizeddi-unsaturated acid esters as well as epoxidized unsaturated polyester,so long as they contain more than one oxirane group per molecule. Thepolyepoxides may be monomeric or polymeric.

Preferred polyepoxides are glycidyl polyethers of polyhydric alcohols orphenols having weights per epoxide group of about 150 to 2000. Thepolyepoxides may be nuclearly substituted with halogen, preferablybromine. These polyepoxides are usually made by reacting at least abouttwo moles of an epihalohydrin or glycerol dihalohydrin with one mole ofthe polyhydric alcohol or polyhydric phenol and a sufficient amount of acaustic alkali to combine with the halogen of the halohydrin. Theproducts are characterized by the presence of more than one epoxidegroup per molecule, i.e., a 1,2-epoxy equivalency greater than one.

Vinyl ester resins are commercially available from The Dow ChemicalCompany under the trademark DERAKANE.

Any polymerizable ethylenically unsaturated monomer can be used herein.Such monomers include both monovinyl and polyvinyl monomers. Typicalmonomers include the alkenyl aromatic monomers such as styrene,α-methylstyrene, chlorostyrene, divinylbenzene, vinyltoluene,t-butylstyrene, and the like; and alkyl and hydroxyalkyl esters ofacrylic and methacrylic acid such as the methyl, ethyl, propyl, butyl,cyclohexyl, and hydroxyethyl esters. In addition to the above, othermonomers that are especially useful for ultraviolet light curablesystems such as 2-acetoxyalkyl acrylates, pentaerythritol di-, tri-, ortetra-acrylate may be used.

Suitable curing agents which can be employed to cure the compositions ofthe present invention include, for example, free radical formingcatalysts. Examples of these catalysts are benzoyl peroxide, tertiarybutyl peroxide, methylethyl ketone peroxide, and the like. It isfrequently of value to add accelerators such as cobalt naphthenate,dimethylaniline, and the like.

The compositions of the present invention are useful in the preparationof castings, laminates, coatings and the like.

The following examples are illustrative of the invention but are not tobe construed as to limiting the scope thereof in any manner.

EXAMPLE 1

A transcarbonation reaction was used to prepare the bis(allylether) ofdicyclopentadiene diphenol, as follows:

Allyl alcohol (48.7 grams, 0.84 mole), dimethyl carbonate (75.6 grams,0.84 mole), and sodium methoxide catalyst (0.10 gram) were added to areactor and maintained at room temperature (25° C.) with stirring undera nitrogen atmosphere. An equilibrium mixture of allylmethyl carbonate,diallyl carbonate, and methanol was rapidly formed. After thirty minutes(1800 s), dicyclopentadiene diphenol (24.7 grams, 0.0771 mole),triphenylphosphine (0.60 gram) and 5.0% palladium or carbon (0.20 gram)were added to the reactor and heating was started. The dicyclopentadienediphenol used was a distilled product containing in excess of 95%isomeric dicyclopentadiene diphenols, less than 1% dicyclopentadienemonophenols, with the remainder being isomeric triphenols andbis(dicyclopentadienyl)diphenols. The dicyclopentadiene diphenols wereapproximately 50% ortho and 50% para isomers. The reaction mixture wasmaintained for four hours (14,400 s) at 82° C. and then cooled to roomtemperature. Filtration through Celite, followed by vacuum stripping at100° C. and 10 mm provided a pale-yellow oil (31.3 grams 100% yield).Nuclear magnetic resonance spectroscopy confirmed the product as thebis(allylether) of dicyclopentadiene diphenol. Gas chromatographic-massspectroscopic analysis confirmed the presence of about 95%bis(allylether) of dicyclopentadiene diphenol (Formula I, n=0, A=--CH₂-- CH═CH₂), about 1% monoallylether of dicyclopentadiene monophenol(Formula X, n=0, A=--CH₂ --CH═CH₂), and about 4% of tris(allylether) ofdicyclopentadiene triphenol (Formula IX, n=0, A=--CH₂ --CH═CH₂) andbis(allylether) of bis(dicyclopentadienyl)diphenol (Formula XI, n=0,A=--CH₂ --CH═CH₂) combined.

EXAMPLE 2

A phase transfer catalyzed direct allylation reaction was used toprepare the bis(allylether) of dicyclopentadiene diphenol, as follows:

Dicyclopentadiene diphenol (64.1 grams, 0.20 mole), p-dioxane (200milliliters), water (200 milliliters), sodium hydroxide (16.4 grams,0.41 mole), and 60% aqueous benzyltrimethylammonium chloride catalyst(6.2 grams, 0.02 mole) were added to a reactor with stirring under anitrogen atmosphere. The dicyclopentadiene diphenol was of the samecomposition as that employed in Example 1. The reactor was heated to 85°C. and then allyl chloride (76.5 grams, 1.0 mole) was added dropwiseover six hours (21,600 s). The reactor was cooled to 77° C. andmaintained at this temperature for fourteen hours (50,400 s). Aftercooling to room temperature (25° C.), the reaction mixture wasneutralized with dilute hydrochloric acid, then multiply extracted withtoluene. Vacuum stripping to remove the toluene solvent provided apale-yellow oil (78.0 grams, 96.9% yield). Nuclear magnetic resonancespectroscopy confirmed the product as the bis(allylether) ofdicyclopentadiene diphenol containing less than about 5% of the Claisenrearrangement products of the bis(allylether) of dicyclopentadienediphenol (Formula II, n=0, A=--CH₂ --CH═CH₂ and Formula III, n=0,A=--CH₂ --CH═CH₂). Gas chromatographic-mass spectroscopic analysisconfirmed the presence of about 90% bis(allylether) of dicyclopentadienediphenol (Formula I, n=0, A=--CH₂ --CH═CH₂), about 5% of bisallylateddicyclopentadiene diphenols and trisallylated dicyclopentadiene diphenol(Formula II, n=0, A=--CH₂ --CH═CH₂ ; Formula III, n=0, A=--CH₂ --CH═CH₂; Formula IV, n=0, A=--CH₂ --CH═CH₂) combined, about 1% monoallyletherof dicyclopentadiene monophenol (Formula X, n=0, A=--CH₂ --CH═CH₂) andabout 4% of tris(allylether) of dicyclopentadiene triphenol (Formula X,n=0, A=--CH₂ --CH═CH₂) and bis(allylether) of bis(dicyclopentadienyl)diphenol (Formula XI, n=0, A=--CH₂ --CH═CH₂) combined. Traces of theClaisen rearrangement products of the monoallylether ofdicyclopentadiene monophenol, the tris(allylether) of dicyclopentadienetriphenol and the bis(allylether) of bis(dicyclopentadienyl) diphenolwere also present.

EXAMPLE 3

A dicyclopentadiene modified unsaturated polyesteramide alkyd wasprepared for formulation with styrene and the bis(allylether) ofdicyclopentadiene diphenol from Example 1:

Maleic anhydride (686.42 grams, 7.00 moles) was added to a reactor andheated to a clear, stirred solution maintained at 100° C. under anitrogen atmosphere. Water (127.94 grams, 7.10 moles) was added inducinga maximum exotherm of 135° C. one minute (60 s) later. Fifteen minutes(900 s) the reactor after the initial water addition was air-cooled to121° C. and dicyclopentadiene (277.64 grams, 2.10 moles) was added. Amaximum exotherm of 125° C. resulted two minutes (120 s) later and afteran additional three minutes (180 s), air cooling reduced the reactiontemperature to 120° C. Fifteen minutes (900 s) after the initialdicyclopentadiene addition, a second aliquot of dicyclopentadiene(277.64 grams, 2.10 moles) was added. A maximum exotherm of 124° C.resulted five minutes (300 s) later and after an additional five minutes(300 s), air cooling reduced the reaction temperature to 120° C. A finalaliquot of dicyclopentadiene (277.64 grams, 2.10 moles) was addedfifteen minutes (900 s) after the second dicyclopentadiene addition andthe 120° C. reaction temperature was re-achieved three minutes (180 s)later. Thirty minutes (1800 s) later, propylene glycol (287.66 grams,3.78 moles) and piperazine (36.18 grams, 0.420 mole) were added andnitrogen sparging was increased to four liters per minute, the steamcondenser was started, and the temperature controller was set at 160° C.This temperature was achieved thirty-two minutes (1920 s) later. Aftertwo hours (7200 s), the temperature controller was set at 205° C. andthis temperature was achieved twenty-five minutes (1500 s) later. Afterfourteen hours (50,400 s), 151.5 milliliters of water layer and 32milliliters of organic material were recovered into the Dean Stark trap.The reactor was cooled to 168° C. and 100 ppm of hydroquinone was added.The modified polyesteramide alkyd was recovered as a clear, light-yellowcolored solid with a final acid number of 18.8.

A portion of the modified unsaturated polyesteramide (199.5 grams),styrene (115.5 grams), and the bis(allylether) of dicyclopentadienediphenol (35.0 grams) from Example 1 were formulated to provide a 57.0,33.0, 10.0% solution, respectively. This solution was used to determinethe Brookfield viscosity (25° C.), SPI (84° C.) gel and cure times plusmaximum exotherm, and a clear, unfilled casting was prepared for use inmechanical property evaluations. A cure system of 1.0% benzoyl peroxideand 0.01% dimethylaniline was used at room temperature (25° C.),followed by post-curing for two hours (7200 s) at 200° F. (93° C.).Tensile test pieces (eight) and flexural test pieces (six) were preparedfrom the clear, unfilled casting and tested using an Instron machinewith standard methods (ASTM D-638 and D-790). A pair of heat distortiontemperature test pieces were prepared from the clear, unfilled castingand tested using an Aminco Plastic Deflection Tester (AmericanInstrument Co.) with standard methods (ASTM D-648). All Barcol hardnessvalues are on the 934-1 scale. The results are reported in Table I.

EXAMPLE 4

A portion of the modified unsaturated polyesteramide (199.5 grams) fromExample 3, styrene (133.0 grams), and the bis(allylether) ofdicyclopentadiene diphenol (17.5 grams) from Example 2 were formulatedto provide a 57.0, 38.0, 5.0% solution, respectively. The physical andmechanical properties were evaluated using the method of Example 3. Theresults are reported in Table I.

COMPARATIVE EXPERIMENT A

A portion of the modified polyesteramide (199.5 grams) from Example 3and styrene (150.5 grams) were formulated to provide a 57.0, 43.0%solution, respectively. The physical and mechanical properties wereevaluated using the method of Example 3. The results are reported inTable I.

                  TABLE I                                                         ______________________________________                                                                       Comp.                                                       Ex. 3   Ex. 4     Expt. A                                        ______________________________________                                        Brookfield Viscosity (cp)                                                                    811       531       241                                        SPI Gel Test                                                                  Gel time, min/sec                                                                            6.0/360   3.6/216   3.3/198                                    Cure time, min/sec                                                                           9.4/564   5.7/342   5.2/312                                    Maximum exotherm (°C.)                                                                153       200       216                                        Average Barcol Hardness                                                                       19        43        43                                        Heat Distortion Tempera-                                                                     163/72.8  209/98.3   231/110.6                                 ture, °F./°C.                                                   Tensile Strength, psi                                                                         5,900     5,800     4,300                                     kPa            40,700    40,000    29,600                                     Elongation (%) 2.7       1.5       1.0                                        Flexural Strength, psi                                                                       10,200    13,800    11,600                                     kPa            70,300    95,100    80,000                                     Flexural Modulus, psi                                                                        260,000   560,000   550,000                                    kPa            1,800,000 3,860,000 3,800,000                                  ______________________________________                                    

EXAMPLE 5

A bisallylated dicyclopentadiene diphenol wherein the allyl groups werelocated solely on the aromatic rings was prepared as follows:

The transcarbonation reaction of Example 1 was scaled up fourfold andrepeated to provide the bis(allylether) of dicyclopentadiene diphenol.The bis(allylether) of dicyclopentadiene diphenol was then added to areactor and maintained with stirring under a nitrogen atmosphere andheating was started. The reaction was maintained for 1 hour (3600 s) at200° C. then cooled to 100° C. and the product recovered while stillfluid. The product was recovered as a clear, light amber-colored solidin quantitative yield. Nuclear magnetic resonance spectroscopy confirmedthe product as bisallylated dicyclopentadiene diphenol wherein the allylgroups were both located solely on the aromtic rings (Formula II, n=0,A=--CH₂ --CH═CH₂). Gas chromatographic-mass spectroscopic analysisdemonstrated that the minor components (Formulas IX, X and XI all wheren=0, A=--CH₂ --CH═CH₂) were present in the proportions indicated byExample 1, however, they were converted to the corresponding isomericallylated phenols during the thermally induced Claisen rearrangement.

EXAMPLE 6

A portion of the bisallylated dicyclopentadiene diphenol of Example 5was converted to a tetraallylated dicyclopentadiene diphenol as follows:

Allyl alcohol (71.92 grams, 1.24 moles), dimethyl carbonate (111.6grams, 1.24 moles), and sodium methoxide catalyst (0.15 gram) were addedto a reactor and maintained at room temperature (25° C.) with stirringunder a nitrogen atmosphere. An equilibrium mixture of allylmethylcarbonate, diallyl carbonate, and methanol was rapidly formed. Afterthirty minutes (1800 s), bisallylated dicyclopentadiene diphenol (50.0grams, 0.124 mole) from Example 5, triphenylphosphine (0.477 gram), and5.0% palladium on carbon (0.32 gram) were added to the reactor andheating was started. The reaction mixture was maintained for four hours(14,400 s) at 80° C. and then cooled to room temperature (25° C.).Filtration through Celite, followed by vacuum stripping at 100° C. and10 mm provided a clear, yellow-colored oil (59.85 grams, 99.6% yield).Nuclear magnetic resonance spectroscopy confirmed the product as thetetraallylated dicyclopentadiene diphenol wherein two of the allylgroups were present as ether-linked substituents and two of the allylgroups were present as substituents on the aromatic rings (Formula VI,n=0, A=--CH₂ --CH═CH₂).

EXAMPLE 7

An orthophthalate unsaturated polyester alkyd was prepared forformulation with styrene and the tetraallylated dicyclopentadienediphenol from Example 6:

Maleic anhydride (176.51 grams, 1.80 moles) and phthalic anhydride(177.74 grams, 1.20 moles) were added to a reactor and heated to awhite, stirred slurry maintained at 100° C. under a nitrogen atmosphere.Propylene glycol (251.13 grams, 3.30 moles) was added and a maximumexotherm of 135° C. occurred twenty-five minutes (1500 s) later. At thistime, nitrogen sparging was increased to one liter per minute, the steamcondenser was started, and the temperature controller was set at 160° C.This temperature was achieved seven minutes (420 s) later. After twohours (7200 s), the temperature controller was set at 205° C. and thistemperature was achieved nineteen minutes (1140 s) later. After fourhours (14,400 s), 56 milliliters of water layer was recovered into theDean Stark trap. The reactor was cooled to 168° C. and 100 ppm ofhydroquinone was added. The unsaturated polyester alkyd was recovered asa transparent solid with a final acid number of 32.4.

A portion of the unsaturated polyester (199.5 grams), styrene (133.0grams), and the tetraallylated dicyclopentadiene diphenol (17.5 grams)for Example 6 were formulated to provide a 57.0, 38.0, 5.0% solution,respectively. The physical and mechanical properties were evaluatedusing the method of Example 3. The results are reported in Table II.

COMPARATIVE EXPERIMENT B

A portion of the unsaturated polyester (199.5 grams) from Example 7 andstyrene (150.5 grams) were formulated to provide a 57.0, 43.0% solution,respectively. The physical and mechanical properties were evaluatedusing the method of Example 3. The results are reported in Table II.

                  TABLE II                                                        ______________________________________                                                                Comp.                                                                 Ex. 7   Expt. B                                               ______________________________________                                        Brookfield Viscosity (cp)                                                                       282       141.5                                             SPI Gel Test                                                                  Gel time, min/sec 2.6/156   2.4/144                                           Cure time, min/sec                                                                              4.4/264   4.0/240                                           Maximum exotherm (°C.)                                                                   194       229                                               Average Barcol Hardness                                                                          40        46                                               Heat Distortion Tempera-                                                                        172/77.8  204/95.6                                          ture, °F./°C.                                                   Tensile Strength, psi                                                                            8,700     8,300                                            kPa               60,000    57,200                                            Elongation (%)    2.6       1.8                                               Flexural Strength, psi                                                                          17,500    21,100                                            kPa               120,700   145,500                                           Flexural Modulus, psi                                                                           530,000   610,000                                           kPa               3,650,000 4,210,000                                         ______________________________________                                    

EXAMPLE 8

A pair of 5.0 by 0.5 by 0.125 inch (12.7 by 1.27 by 0.318 cm) testpieces were prepared from the clear, unfilled castings of both Example 7and Comparative Experiment B. The two sets of test pieces were placed ona flat aluminum tray and suspended in a forced air, convection-typeoven. An additional curing cycle of three hours (10,800 s) at 94° C.,two hours (7200 s) at 125° C., and three hours (10,800 s) at 175° C. wascompleted. After this additional curing, the initial weight of each testpiece was obtained. The test pieces were then placed back in the ovenand maintained at 175° C. They were removed and weighed after 15 and 39hours (54,000 and 140,400 s) of exposure. After the 39 hour (140,400 s)interval, the exposure temperature was increased to 200° C. and the testpieces were removed and weighed after 48 total hours (172,800 s) ofexposure. The results are reported in Table III wherein the weight lossis expressed as the percent of the initial weight of each respectivetest piece.

                  TABLE III                                                       ______________________________________                                                    Percent Weight Loss                                                                           Comparative                                       Total Hours/Seconds                                                                         Example 7      Experiment B                                     of Thermal Exposure                                                                         1       2         1     2                                       ______________________________________                                        15/54,000     -0.46   -0.44     -0.61 -0.63                                   39/140,400    -0.67   -0.65     -1.03 -1.06                                   48/172,800    -1.76   -1.72     -2.89 -2.89                                   ______________________________________                                    

EXAMPLE 9

A series of 5.0 by 0.5 by 0.125 inch (12.7 by 1.27 by 0.318 cm) heatdistortion temperature test pieces were prepared from the clear,unfilled castings of both Example 4 and Comparative Experiment A. Thetest pieces were placed on a flat aluminum tray which was then suspendedin a forced-air, convection-type oven. Further curing at 94° C. forthree hours (10,800 s) and 125° C. for two hours (7200 s) was completed,followed by heat aging for the indicated times and temperaturessummarized in Table IV. Test pieces were removed at the indicatedexposure intervals and the heat distortion temperatures were determinedusing the method of Example 3. The results are reported in Table IV.

                  TABLE IV                                                        ______________________________________                                                          Heat Distortion                                                              Temperature (°F./°C.)                          Total Hours/Sec of                                                                        Temperature                                                                              Example   Comparative                                  Thermal Exposure                                                                          (°C.)                                                                             4         Experiment A                                 ______________________________________                                         3/10,800   175        260/126.7 295/146.1                                     15/54,000  175        286/141.1 310/154.4                                     39/140,400 175        295/146.1 313/156.1                                     75/270,000 200        324/162.2 319/159.4                                    138/496,800 200        329/165.0 338/170.0                                    154/554,400 200        340/171.1 353/178.3                                    178/640,800 200        350/176.7 338/170.0                                    ______________________________________                                    

EXAMPLE 10

A portion of the tetraallylated dicyclopentadiene diphenol from Example6 was partially brominated, as follows:

Tetraallylated dicyclopentadiene diphenol (36.56 grams, 0.0761 mole)from Example 6 and methylene chloride (250 grams) were added to areactor and maintained under a nitrogen atmosphere with stirring. Thereactor was chilled using a methylene chloride-dry ice bath. Bromine(36.47 grams, 0.2282 mole) was added dropwise to the solution over asix-minute (360 s) period during which time the reaction temperature waskept between minus 5° to 10° C. After an additional fifteen minutes (900s) at the the minus 10° C. reaction temperature, 1.0 percent by weightof the diglycidyl ether of a polyglycol (sold commercially as D.E.R.®736epoxy resin) having an epoxy equivalent weight of 175-205 was added as ahydrohalide scavenger then the reactor was allowed to warm to roomtemperature (25° C.). Vacuum stripping at 75° C. and 10 mm provided anamber-colored solid (58.80 grams), wherein about 1.8 allyl groups permolecule of tetraallylated dicyclopentadiene diphenol were converted todibromopropane groups. Nuclear magnetic resonance spectroscopy was usedto confirm the product structure (Formula VI, n=0, A=(major) ##STR6##where X=Br and (minor) --CH₂ --CH═CH₂).

EXAMPLE 11

A portion of the dicyclopentadiene modified unsaturated polyesteramide(30.0 grams) of Example 3 was formulated with styrene (30.0 grams) and aportion of the partially brominated tetraallylated dicyclopentadienediphenol of Example 10 to provide a 40.0, 40.0, 20.0 percent solution,respectively. The formulation was used to prepare a clear, unfilledcasting. A cure system of 2.0% benzoyl peroxide and 0.01%dimethylaniline was used at room temperature (25° C.), followed bypost-curing for two hours (7200 s) at 200° F. (93° C.). Test pieces wereprepared from the clear, unfilled casting and used with standard methods(ASTM D-2863-76) to determine oxygen index. The oxygen index value was26.75.

EXAMPLE 12

A vinyl ester resin was prepared for formulation with thebis(allylether) of dicyclopentadiene diphenol:

About 1 equivalent of methacrylic acid is reacted with 0.75 equivalentof an epoxy novolac having an epoxide equivalent weight (EEW) of 175-182and 0.25 equivalent of a glycidyl polyether of bisphenol A having an EEWof 186-192. The above reactants are heated to 115° C. with catalyst andhydroquinone present until the carboxylic acid content reaches about 1percent. The reactants are cooled and then styrene (containing 50 ppm oft-butyl catechol) is added. The final vinyl ester resin diluted withstyrene has a pH of 7.7 and contains approximately:

    ______________________________________                                        Contents          %                                                           ______________________________________                                        styrene           36                                                          methacrylic acid  20.6                                                        epoxy novolac     32.1                                                        (EEW = 175-182)                                                               diglycidyl ether of                                                                             11.3                                                        bisphenol A (EEW =                                                            186-192)                                                                                        100.00                                                      ______________________________________                                    

A portion of the styrenated vinyl ester resin (300.0 grams) and thebis(allylether) of dicyclopentadiene diphenol (22.58 grams) wereformulated to provide a 93.0, 7.0% solution, respectively. Thebis(allylether) of dicyclopentadiene diphenol used in this formulationwas prepared using the method of Example 1. The physical and mechanicalproperties of the resin formulation were determined using the method ofExample 3. The results are reported in Table V.

COMPARATIVE EXPERIMENT C

A portion of the styrenated vinyl ester resin of Example 12 was used todetermine physical and mechanical properties using the method of Example3. The results are reported in Table V.

                  TABLE V                                                         ______________________________________                                                                Comp.                                                                 Ex. 12  Expt. C                                               ______________________________________                                        Brookfield Viscosity (cp)                                                                       295       260                                               SPI Gel Test                                                                  Gel time, min/sec 12.0/720  8.0/480                                           Cure time, min/sec                                                                              15.8/948  9.5/570                                           Maximum exotherm (°C.)                                                                   178       209                                               Average Barcol Hardness                                                                          42        39                                               Heat Distortion Tempera-                                                                        201/93.9   214/101.1                                        ture, °F./°C.                                                   Tensile Strength, psi                                                                           10,800     9,000                                            kPa               74,500    62,100                                            Elongation (%)    2.8       2.8                                               Flexural Strength, psi                                                                          21,700    19,200                                            kPa               149,600   132,400                                           Flexural Modulus, psi                                                                           660,000   640,000                                           kPa               4,550,000 4,410,000                                         ______________________________________                                    

EXAMPLE 13

A mixture of an unsaturated polyester alkyd, a dicyclopentadienemodified unsaturated polyesteramide alkyd and a vinyl ester resin wereprepared for formulation with styrene and the bis(allylether) ofdicyclopentadiene diphenol.

Tetrahydrophthalic anhydride (456.45 grams, 3.00 moles), maleicanhydride (294.18 grams, 3.00 moles), propylene glycol (251.13 grams,3.30 moles) and dipropylene glycol (442.79 grams, 3.30 moles) werecondensed to provide an unsaturated polyester alkyd with a final acidnumber of 25.4. A portion of this unsaturated polyester alkyd (25.0grams), the modified unsaturated polyesteramide (114.0 grams) fromExample 3, the styrenated vinyl ester resin (50.0 grams) from Example12, styrene (86.0 grams) and bis(allylether) of dicyclopentadienediphenol (18.5 grams) prepared using the method of Example 1 wereformulated to provide the following solution:

    ______________________________________                                                          Percent by                                                                    Weight                                                      ______________________________________                                        unsaturated polyester                                                                             8.52                                                      dicyclopentadiene modified                                                                        38.84                                                     unsaturated polyesteramide                                                    vinyl ester (active)                                                                              10.90                                                     styrene             35.44                                                     bis(allylether) of dicyclopenta-                                                                  6.30                                                      diene diphenol                                                                ______________________________________                                    

The physical and mechanical properties were evaluated using the methodof Example 3. The results are reported in Table VI.

COMPARATIVE EXPERIMENT D

A portion of the unsaturated polyester alkyd (25.0 grams) from Example13, the modified unsaturated polyesteramide (114.0 grams) from Example3, the styrenated vinyl ester resin (50.0 grams) from Example 12 andstyrene (104.5 grams) were formulated to provide the following solution:

    ______________________________________                                                         Percent by                                                                    Weight                                                       ______________________________________                                        unsaturated polyester                                                                            8.52                                                       dicyclopentadiene modified                                                                       38.84                                                      unsaturated polyesteramide                                                    vinyl ester (active)                                                                             10.90                                                      styrene            41.74                                                      ______________________________________                                    

The physical and mechanical properties were evaluated using the methodof Example 3. The results are reported in Table VI.

                  TABLE VI                                                        ______________________________________                                                                 Comp.                                                                 Ex. 13  Expt. D                                              ______________________________________                                        Brookfield Viscosity (cp)                                                                        208       97                                               SPI Gel Test                                                                  Gel time, min./sec.                                                                              11.2/672  6.7/402                                          Cure time, min./sec.                                                                             15.7/942  9.2/552                                          Maximum exotherm (°C.)                                                                    160       216                                              Average Barcol Hardness                                                                           42        45                                              Heat Distortion Temperature,                                                                     174/79    234/112                                          °F./°C.                                                         Tensile Strength, psi                                                                             8,926     7,241                                           kPa                61,543    49,925                                           Elongation (%)     2.54      1.69                                             Flexural Strength, psi                                                                           15,729    15,539                                           kPa                108,448   107,138                                          Flexural Modulus, psi                                                                            500,000   574,000                                          kPa                3,447,400 3,957,615                                        ______________________________________                                    

I claim:
 1. A composition which is thermosettable upon curing with acuring quantity of a suitable curing agent, which thermosettablecomposition comprises,(1) from 5 to about 95 percent by weight (pbw) ofat least one resin composition selected from the group consisting of(a)unsaturated polyester resins, (b) unsaturated polyesteramide resins, (c)dicyclopentadiene modified unsaturated polyester resins, (d)dicyclopentadiene modified unsaturated polyesteramide resins, and (e)vinyl ester resins, (2) from zero to about 95 pbw of at least onepolymerizable ethylenically unsaturated monomer; and (3) from about 1 toabout 50 pbw of a composition represented by Formulas I throughXI;wherein each A is independently --CH₂ --CH═CH₂ or ##STR7## whereineach X is a halogen and each n independently has a value of from zero toabout
 20. 2. A composition of claim 1 wherein(a) component (1) ispresent in quantities of from about 20 to about 80 pbw; (b) component(2) is present in quantities of from about 70 to about 20 pbw; and (c)component (3) is present in quantities of from about 1 to about 30 pbw.3. A composition of claim 2 wherein(a) component (1) is present inquantities of from about 45 to about 70 pbw; (b) component (2) ispresent in quantities of from about 30 to about 55 pbw; and (c)component (3) is present in quantities of from about 3 to about 15 pbw.4. A composition of claims 1, 2 or 3 wherein(a) component (1) containsat least one of components (1-a), (1-c), (1-d) or (1-e); (b) component(2) contains styrene; and (c) component (3) is a composition wherein atleast 90% by weight is represented by Formulas I, II, III, IV, V, VI,VII or VIII.
 5. A composition of claim 4 wherein in component (3), saidcomposition is represented by Formula I, A is --CH₂ --CH═CH₂ and n hasan average value of from zero to about
 20. 6. A composition of claim 5wherein n is zero.
 7. A composition of claim 4 wherein in component (3)at least 10% of the A groups are ##STR8## X is chlorine or bromine and nhas an average value of from zero to about
 20. 8. A composition of claim7 wherein X is bromine and n is zero.
 9. A composition of claim 4wherein component (3) is a composition represented by Formula II, A is--CH₂ --CH═CH₂ and n has an average value of from zero to about
 20. 10.A composition of claim 9 wherein n is zero.
 11. A composition of claim 9wherein in component (3) said composition is represented by Formula II,at least 10% of the A groups are ##STR9## X is chlorine or bromine and nhas an average value from zero to about
 20. 12. A composition of claim11 wherein X is bromine and n is zero.
 13. A composition of claim 4wherein in component (3) said composition is represented by Formula VI,A is --CH₂ --CH═CH₂ and n has an average value of from zero to about 20.14. A composition of claim 13 wherein n is zero.
 15. A composition ofclaim 13 wherein in component (3) said composition is represented byFormula VI, at least 10% of the A groups are ##STR10## X is chlorine orbromine and n has an average value from zero to about
 20. 16. Acomposition of claim 15 wherein n is zero.
 17. A cured composition ofclaims 1, 2, 3 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or
 16. 18. A curedcomposition of claim 4.